Composition for producing wrinkle-free permanently pressed cellulosic textile materials

ABSTRACT

A COMPOSITION USEFUL FOR IMPARTING ABRASION RESISTANCE, RESISTANCE TO FROSTING, WRINKLE RESISTANCE, CREASE RETENTION, WASH-AND-WEAR CHARACTERISTICS, DURABLE PRESS CHARACTERISTICS, AND PERMANENT PRESS CHARACTERISTICS TO CELLULOSIC TEXTILE MATERIALS AND TO IMPROVE THE WET STRENGTH, WATER ABSORPTION, AND OTHER PROPERTIES OF CELLULOSIC PAPER. THE COMPOSITION COMPRISES AN AQUEOUS AMINOPLAST SYSTEM ADMIXED WITH AN EFFECTIVE AMOUNT OF A MEMBER OF A FIRST GROUP CONSISTING OF:   R1-C(-R2)(-OR3)-(CH2)X-CO-N(-R4)-R5 AND R1-C(-R2)(-OH)-   (CH2)X-CO-A   WHERE; (A) X IS 0 OR 1; (B) R1 IS HYDROEN OR AN ALKYL GROUP HAVING ABOUT 1-5 CARBON ATOMS; (C) R2 IS HYDROGEN OR AN ALKYL GROUP HAVING ABOUT 1-5 CARBON ATOMS; (D) R3 IS HYDROGEN, AN ALKYL GROUP HAVING ABOUT 1-5 CARBON ATOMS, OR -SO3-, (E) R4 IS HYDROGEN, AN ALKYL GROUP HAVING ABOUT 1-8 CARBON ATOMS, -CH2CH2OH; OR -C6H5; (F) R5 IS HYDROGEN, AN ALKYL GROUP HAING ABOUT 1-8 CARBON ATOMS, -CH2CH2OH; -C6H5; OR -CH2OH; AND (G) A IS A MEMBER SELECTED FROM A SECOND GROUP CONSISTING OF; (I) -NC5H10; (II) -NC4H8O; AND (III) -NC4H8.

United States Patent 3,827,994 COMPOSITION FOR PRODUCING WRlNKLE-FREE PERMANENTLY PRESSED CELLULOSIC TEX- TILE MATERIALS Robert J. Cicione, Cranston, R.I., and Edward G. Nagar, Lincoln, Patricia M. Scanlon, Arlington, John L. Ohlson, Bedford, and Joseph F. Finn, Hyde Park, Mass., assignors to W. R. Grace & C0,, New York,

Nb brawing. Filed Nov. 4, 1911, Ser. No. 195,844 Int. (:1. C08g 51/24 U.S. Cl. 260-29.4 R 15 Claims ABSTRACT OF THE DISCLOSURE where; (a) x is 0 or 1; (b) R is hydrogen or an alkyl group having about 1-5 carbon atoms; (0) R is hydrogen or an alkyl group having about 1-5 carbon atoms; (d) R is hydrogen, an alkyl group having about 1-5 carbon atoms, or -SO (e) R, is hydrogen, an alkyl group having about 1-8 carbon atoms, CH CH OH; or -C H (f) R is hydrogen, an alkyl group having about 1-8 carbon atoms, CH CH OH; -C H or CH OH; and (g) A is a member selected from a second group consisting of; (i) -NC H (ii) -NC H O; and (iii) NC H BACKGROUND OF THE INVENTION This invention is in the field of cellulosic textile materials and cellulosic paper. More particularly, this invention is in the field of; (a) crease resistant, durable press, or permanent press cellulosic textiles; and (b) cellulosic paper with superior physical properties.

As directed to cellulosic textile materials, this invention is concerned with processes, compositions, and agents for treating cellulosic textile materials to render said materials crease resistant, to make them excellently adapted to receiving and retaining a permanent press, and excellently adapted for use as; (a) wash-and-wear and permanent press clothing; and (b) crease resistant and permanent press sheets, pillow cases, curtains, and the like. Cellulosic textile materials which have been treated according to this invention have an excellent hand; they also have an abrasion resistance and a tear resistance superior to that of the same cellulosic textile material treated with an aminoplast creaseproofing agent that does not contain a member of the first group recited in the following summary.

The aqueous aminoplast creaseproofing agent (ACA) of our invention comprises an aqueous solution or an aqueous suspension containing an aminoplast, an acidic catalyst (acidic curing catalyst) for curing the aminoplast, and an effective amount of the first group member recited in said summary. Said ACA can also contain one or more other additives such as brighteners, softeners, wetting agents, chelating agents, and the like. Said ACA can be cured by heating or by irradiation.

'ice

Incorporating said first group member into an ACA causes clothing, sheets, curtains, and the like made from a cellulosic textile material which has been impregnated with said ACA, dried, and cured to have a far better hand, a greater abrasion resistance, a greater crease recovery, a greater tensile strength, an excellent shrink resistance, and less frosting than clothing, sheets, curtains, and the like made from the same lot of cellulosic textile material treated With the ACA which has not had an effective amount of said first group member incorporated therein.

The aqueous aminoplast composition (AAC) of our invention comprises an aqueous solution or aqueous suspension containing an aminoplast and an effective amount of the first group member recited in said summary. Said AAC can also contain one or more other additives such as brighteners, softeners, wetting agents, chelating agents, and the like, but said AAC is substantially free of acidic curing catalyst (acidic catalyst). Said AAC can be cured by irradiation or by heating in the presence of an acidic catalyst (e.g., S0 HCl, HBr, or the like).

Incorporating said first group member into an AAC causes clothing, sheets, curtains, and the like made from a cellulosic textile material which has been impregnated with said AAC, dried, and cured to have a far better hand, a greater abrasion resistance, a better crease recovery, a greater tensile strength, an excellent shrink resistance, and less frosting then clothing, sheets, curtains, and the like made from the same lot of cellulosic textile material which has been treated with the AAC which has not had an effective amount of said first member incorporated therein.

The reason for these unexpected beneficial results is not understood especially since Frick et al., U.S. Pat. No. 3,144,299 (8/ 116.3) teach that a finishing agent for cellulosic textile material must have 2 or more methylol groups per molecule and We have found that no member of said first group has more than one methylol group per molecule and many members of said first group do not contain a methylol group.

Prior art methods and prior art systems for treating cellulosic textile materials to make said materials crease resistant and to give them durable press and permanent press characteristics are well known to those skilled in the art. Among the many references which teach methods and systems useful for this purpose are the following U.S. patents:

The use of aqueous aminoplast systems to improve the physical properties of paper is also well known to those skilled in the art. Where used to treat cellulosic paper, an ACA is often called an aqueous aminoplast paper treating agen a terminology which we have adopted and which we use in our claims. Where used to treat cellulosic paper an AAC is often called an aqueous aminoplast paper treating compositiona terminology which we have adopted and which we use in our claims.

The ACA, AAC, aqueous aminoplast paper treating agent, and aqueous aminoplast paper treating composition of this invention can contain up to about 50% or more of at least one water soluble non-aqueous solvent such as dioxane, methyl alcohol, ethyl alcohol, isopropyl alcohol, propyl alcohol, dimethylformamide, dimethyl sulfoxide, and the like.

The process, ACA, and AAC of our invention are use- 1.11 for preparing permanent press, creaseproof, and washand-wear clothing and for preparing permanent press and creaseproof fabric for use in making articles such as pillow cases, bed sheets, tablecloths, drapes, window curtains, and the like.

This invention is also in the field of cellulosic paper and the treatment of said paper with aqueous aminoplast systems (which can contain up to about 50% or more of at least one non-aqueous solvent such as dioxane, methyl alcohol, dimethylformamide, dimethylsulfoxide, propyl alcohol, ethyl alcohol, and the like) to improve the papers propertiesespecially its wet strength and water absorbence.

The treated paper is especially useful as paper toweling, wet strength wrapping paper, and the like.

Where using an aqueous aminoplast composition (AAC) to treat paper, the composition is often called an aqueous aminoplast paper treating composition a terminology which we use in our claims.

Where using an aqueous aminoplast creaseproofing agent (ACA) to treat paper, the agent is often called an aqueous aminoplast paper treating agenta terminology which we use in our claims.

Objects of this invention include providing; (a) agents, compositions, and processes useful for preparing crease resistant, wash-and-wear, permanent press, and durable press cellulosic textile fabrics having a high abrasion resistance, excellent wrinkle resistance, excellent dimension stability, high tear resistance, excellent tensile strength, substantial freedom from frosting, and an excellent hand; and (b) agents, compositions, and processes for preparing paper with superior physical properties. Still other objects will be readily apparent to those skilled in the art.

SUMMARY OF THE INVENTION In summary, this invention is directed to a composition of matter (an improved aqueous aminoplast creaseproofing agent (ACA) of our invention) prepared by admixing an aqueous aminoplast creaseproofing agent and an effective quantity of a member selected from a first group consisting of;

where;

(a) x is O or 1;

(b) R is hydrogen or an alkyl group having about 1-5 carbon atoms;

() R is hydrogen or an alkyl group having about 1-5 carbon atoms;

(d) R is hydrogen, an alkyl group having about 1-5 carbon atoms, or SO (e) R, is hydrogen, an alkyl group having about 1-8 carbon atoms,

(f) 'R is hydrogen, an alkyl group having about 1-8 carbon atoms,

-onicnion; or -cn1oH;

and

(g) A is a member selected from a second group consisting of;

( CHr-CH:

N CH3;

CHg-CH and (iii) CHI-on,

the ACA containing an effective amount (or quantity) of aminoplast.

DESCRIPTION OF PREFERRED EMBODIMENTS In preferred embodiments of the composition set forth in the above summary:

(1) x is 0; R is CH and R R R and R are hydrogen.

(2) x is 0; R is CH R is hydrogen; R is SO R is H; and R is H, or CH OH.

(3) x is 0, R is -CH R R and R are hydrogen; and R is CHOH.

This invention is also directed to:

(1) A composition consisting essentially of a cellulosic textile material wetted with about 10-100% of the composition of the above summary.

(2) A composition consisting essentially of a cellulosic textile material wetted with about 10-100% of the composition of the above summary and then dried.

(3) A composition consisting essentially of a cellulosic textile material wetted with about 10-100% of the composition of the above summary, dried, and then cured by; (a) heating; or (b) irradiating (e.g., with infrared, ultraviolet, gamma rays, X-rays, an electron beam, a neutron beam, or a proton beam).

In another preferred embodiment (Embodiment A) this invention is directed to an improved aqueous aminoplast composition (AAC) prepared by admixing an aqueous aminoplast solution which is substantially free of acidic catalyst and which can contain a wetting agent, a brightener, a softener, and a chelating agent; the brightener and/or softener can be substantially insoluble in water causing the solution to actually be a dispersion with the aminoplast and first group member dissolved in the aqueous phase of the dispersion and an efiective quantity of a member selected from a first group consisting of;

where;

(a) x is O or 1;

(b) R is hydrogen or an alkyl group having about l-S carbon atoms;

(0) R is hydrogen or an alkyl group having about 1-5 carbon atoms;

(d) R; is hydrogen, an alkyl group having about 1-5 carbon atoms, or SO;;

(e) R is hydrogen, an alkyl group having about 1-8 carbon atoms,

(E) R is hydrogen, an alkyl group having about 1-8 carbon atoms,

and (g) A is a member selected from a second group consisting of;

(i) CH3CH2 N CH2;

and

( CH:CH2

the AAC containing an effective amount (or quantity) of aminoplast.

In especially preferred embodiments of the composition set forth in Embodiment A, supra;

1) x is R is CH and R2, R R and R are hydrogen.

(2) x is 0; R is CH R is hydrogen; R is SO R is H; and R is H or -CH OH.

(3) x is 0; R is -CH R R and R are hydrogen and R is CH OH.

This invention is also directed to:

(l) A composition consisting essentially of a cellulosic textile material wetted with about 100% of the composition of Embodiment A, supra.

(2) A composition consisting essentially of a cellulosic textile material wetted with about 10100% of the composition of Embodiment A, supra, and then dried.

(3) A composition consisting essentially of a cellulosic textile material Wetted with about 10-100% of the composition of Embodiment A, supra, dried, and then cured by; (a) irradiating (e.g., with infrared, ultraviolet, or high energy radiation such as X-rays, gamma rays, an electron beam, a proton beam, or a neutron beam); or (b) by heating in the presence of an acid catalyst (e.g., HCl, HBr, S0 formic acid vapor, and the like).

In another preferred embodiment (Embodiment B) this invention is directed to a composition prepared by impregnating a cellulosic textile material with an effective amount (e.g., preferably about 100%) of an aqueous solution of a member selected from a first group consisting of;

(a) x is 0 or 1;

(b) R is hydrogen or an alkyl group having about 1-5 carbon atoms;

(c) R is hydrogen or an alkyl group having about 1-5 carbon atoms;

(d) R is hydrogen, an alkyl group having about 1-5 carbon atoms, or SO (e) R, is hydrogen, an alkyl group having about l8 carbon atoms,

(f) R is hydrogen, an aklyl group having about 1-8 carbon atoms;

6 and (g) A is a member selected from a second group consisting of;

(i) CH:CH2

--N CH2;

( i) CH1CH1 CH -CH;

and

(iii) CH:CH2

OIL-CH2,

said aqueous solution containing an effective amount of the aminoplast.

In especially preferred embodiments of the composition set forth in Embodiment B, supra:

(1) x is 0; R is CH and R R R and R are hydrogen.

(2) x is 0; R is --CH;;; R is hydrogen; R is SO;;*; R is H; and R is H or CH OH.

(3) x is 0; R is CH R R and R are hydrogen; and R is CH OH.

(4) The composition is dried.

(5) The dried composition (the composition of item (4), supra) is cured with formaldehyde (e.g., by heating in the presence of HCHO and an effective quantity of a gaseous acidic catalyst (e.g., HCl, HBr, HI, S0 formic acid vapor, or the like) or by irradiating (e.g., with infrared, ultraviolet, X-rays, gamma rays, an electron beam, a neutron beam, or a proton beam) in the presence of HCHO). The formaldehyde can be conveniently supplied by vaporizing formaldehyde from an aqueous formaldehyde solution, by heating paraformaldehyde or by heating trioxane preferably in the presence of a catalyst such as BF or other cationic catalyst (Lewis acid).

In another preferred embodiment (Embodiment C) this invention is directed to an improvement in a process for manufacturing a garment from a fabric prepared from a cellulosic textile material comprising impregnating the fabric with a heat curable aqueous aminoplast creaseproofing agent (ACA), said heat curable aqueous aminoplast creaseproofing agent consisting essentially of; (a) water; (b) an aminoplast; and (c) an acidic catalyst. Said aminoplast creaseproofing agent (actually the aminoplast component of said agent) is also radiation curable (e.g., it can be cured by irradiation with gamma rays, X-rays, ultraviolet radiation, infra radiation, a neutron beam, a proton beam, or an electron beam). Curing said agent with radiation is fully equivalent to curing it with heat and is encompassed herein. Where curing by radiation, the presence of the acidic catalyst (acidic curing catalyst) does no harm but neither does it (the acidic curing catalyst) serve any useful purpose. Hence, said catalyst need not be present where curing by radiation. However, said catalyst is required where curing by heating. Curing by radiation in the presence or absence of said catalyst is fully equivalent to curing with heat in the presence of said catalyst.

The impregnated fabric is dried at a temperature below the curing temperature of the aminoplast component of the heat curable ACA and then cut to the size, shape and style of the desired garment. The cut fabric is sewed to provide garment seams, and finished to make a completed garment. Creases are imparted into the completed garment consistent with the desired design and style thereof, and thereafter the impregnated, dried, completed, and creased garment is cured by radiation, or it is heated (e.g., to about -205 C. preferably about -200 C.), to cure the aminoplast and insolubilize it in situ so that the completed garment is pressfree and the imparted creases therein are unaffected after repeated washing of the garment, the improvement comprising incorporating into (i.e., admixing with) the heat curable aminoplast creaseproofing agent an effective amount (or quantity) of a member selected from a first group consisting of;

(f) R is hydrogen, an alkyl group having about 1-8 carbon atoms,

on,0n,0n; or 42112011;

and

(g) A is a member selected from a second group consisting of;

CHz-CHg CHzCHz a /GHz-OE; I

the ACA containing an effective amount (quantity) of the aminoplast.

In the process of Embodiment C, supra:

(1) x is 0; R is -CH and R R R and R are hydrogen.

(2) x is 0; R is --CH R is hydrogen; R is SO R is H; and R is H or CH OH.

(3) x is 0; R is CH R R and R are hydrogen; and R5 is --CH30H.

In another preferred embodiment (Embodiment D) this invention is directed to an improvement in a process for treating a cellulosic textile material with an aqueous aminoplast composition (AAC)-an aqueous aminoplast system which is substantially free of acidic curing catalyst and which can contain a softener, a brightener, a wetting agent, a chelating agent, and the like. The process comprises impregnating the cellulosic textile material with the AAC, drying the impregnated cellulosic textile material and curing the aminoplast thereon by maintaining the dried impregnated cellulosic material in the presence of a gaseous acidic catalyst such as a hydrogen halide, S0 or formic acid vapor at a temperature above about 25 C. (preferably at about 5065 C. for about /2 to 60 minutes) or by irradiating the dried impregnated cellulosic textile material with infrared, ultraviolet, X-rays, gamma rays, a proton beam, a neutron beam, or an electron beam; the improvement comprises incorporating into (i.e., admixing with) the AAC an effective amount (or an eifective quantity) of a member selected from a first group consisting of;

R and O H where (a) x is 0 or 1;

(b) R is hydrogen or an alkyl group having about 15 carbon atoms;

(c) R is hydrogen or an alkyl group having about l-S carbon atoms;

(d) R;, is hydrogen, an alkyl group having about 1-5 carbon atoms, or -SO (e) R; is hydrogen, an alkyl group having about 1-8 carbon atoms,

(f) R is hydrogen, an alkyl group having about 1-8 carbon atoms,

cH,oHz0H; or -crnon; and

and

(iii) Caron,

the AAC, after admixing with the first group member, containing an eitective amount of the aminoplast. (See US. Pat. No. 3,518,044, Reinhardt et al., 8/129 and US. Pat. No. 3,450,485, Reinhardt et al., 8/1163.)

In the process of Embodiment D, supra:

(1) x is 0; R is CH and R R R and R are hydrogen.

(2) x is 0; R is CH R is hydrogen; R is SO R is H; and R is H or CH OH.

(3) x is 0; R is -CH R R and R are hydrogen; and R is CH OH.

In another preferred embodiment (Embodiment E) this invention is directed to an improvement in a process for rendering a cellulosic textile material creaseproof by contacting said textile material with a gaseous aldehyde (e.g., formaldehyde, glyoxal, acrolein, and their homologs, see US. Pat. No. 3,528,762, Lauchener, 8/116) and a gaseous acidic catalyst, the improvement comprising impregnating said textile material with a sufficient quantity of an aqueous solution of a member selected from a later recited first group to provide an effective amount of the first group member before contacting the cellulosic textile material with the aldehyde and the gaseous acidic catalyst, the first group consisting of:

(a) xisOor 1;

-cr-ncrnon; or

(f) R is hydrogen, an alkyl group having about 1-8 carbon atoms,

(g) A is a member selected from a second group consisting of:

( CHzCH2 C H -CH and (iii) CH -CH:

CHg Hg the aqueous solution of the first group member contains about 140% (preferably about 5-20%) of the first group member. The aqueous solution of the first group member can contain a wetting agent, a chelating agent, a brightener (i.e., a textile brightener or brightening agent) and a softener (i.e., a textile softener or softening agent). Since the brightener and/or softener can be only slightly soluble (or substantially insoluble) in water it is readily apparent that the aqueous solution of the first group member can actually be an aqueous dispersion of undissolved brightener or softener with the first group member dissolved in the aqueous phase. This process has also been used to improve the physical properties (especially wet strength and rate of water absorption) of cellulosic paper.

In other embodiments of the process set forth in Embodiment E, supra:

(1) Said textile material is dried after being impregnated with said aqueous solution of said first group member and before being contacted with said gaseous aldehyde and said gaseous acidic catalyst (e.g., HCl, HBr, HI, S formic acid vapor, or the like).

(2) x is 0; R is CH and R R R and R are hydrogen.

(3) x is 0; R is CH R is hydrogen; R is 4O3 R is H; and R is H or -CH OH.

(4) x is 0; R is CH R R and R are hydrogen; and R is -CH OH.

In another preferred embodiment (Embodiment F) this invention is directed to an improvement in a process for treating a cellulosic textile material with an aqueous aminoplast creaseproofing agent (ACA)-an aqueous aminoplast system which contains an effective amount of an acidic curing catalyst and which can contain a softener, a brightener, a Wetting agent, a chelating agent, and the like. The process comprises impregnating the cellulosic textile material with the ACA, drying the impregnated cellulosic textile material and curing the aminoplast thereon by maintaining the dried impregnated cellulosic material at about 120205 C., preferably about 150- 200 C.) for about 1-30 minutes (preferably about 2-15- minutes). If desired, vacuum can be used to accelerate the curing step. Alternatively, curing can be produced by irradiating the dried impregnated cellulosic textile material with infrared, ultraviolet, X-rays, gamma rays, a proton beam, or an electron beam. The improvement comprises incorporating into (i.e., admixing with) the ACA an effective amount (i.e., an effective quantity) of a member selected from a first group consisting of:

where;

(a) x is O or 1;

(b) R is hydrogen or an alkyl group having about 1-5 carbon atoms;

(c) R is hydrogen or an alkyl group having about l-S carbon atoms;

(d) R is hydrogen, an alkyl group having about 1-5 carbon atoms, or -SO- (e) R; is hydrogen, an alkyl group having about 1-8 carbon atoms,

(f) R is hydrogen, an alkyl group having about 18 carbon atoms,

-on,oH,oH; or -omorr; and

(g) A is a member selected from a second group consisting of;

( CH;CH

CHa C and (ill) GHQ-CH2 the ACA, after admixing with the first group member, containing about 250% (preferably about 10-30%) aminoplast based on the total weight of the ACA (i.e., original ACA plus first group member plus any solvent (water or non-aqueous solvent which is soluble in water) added with the first group member).

In the process of Embodiment F, supra:

(1) x is 0; R is CH and R R R and R are hydrogen.

(2) x is 0; R is CH R is hydrogen; R is SO R is H; and R is H or -CH OH.

(3) x is 0; R is CH R R and R are hydrogen; and R is CH OH.

In another preferred embodiment (Embodiment G) this invention is directed to an aqueous aminoplast composition (AAC) which is prepared by a process comprising; (a) forming a first mixture by admixing an aminoplast precursor in an amount to provide an effective amount of aminoplast in the final composition, aqueous formaldehyde (the formaldehyde is generally added as an aqueous solution analyzing about 20-50% HCHO; additional water can be added if desired); and an effective amount (quantity) of a member selected from a first group consisting of;

where;

(vi) R is hydrogen, an alkyl group having about 1-8 carbon atoms,

(vii) A is a member selected from a second group consisting of;

CHz-CHZ CHI-CH1 N CH:; N O; and

GHQ-CH1 CH;CH2

out-on,

om-om,

the equivalent ratio of aminoplast precursor to formaldehyde being about 1:1.1-2 (preferably about 121.25- 1.75 )if desired the volume can be adjusted so that the AAC produced contains about 20-80% (preferably about 30-50%) aminoplast; (b) forming a second mixture by adjusting the pH of the first mixture to about 85-105 (the pH can be adjusted by addition of; (1) an alkali metal hydroxide; (2) barium hydroxide; (3) sodium carbonate and/ or potassium carbonate; (4) sodium hydroxide and sodium carbonate and/ or potassium carbonate; or (5) potassium hydroxide and potassium carbonate and/or sodium carbonate, because of solubilities, neither barium hydroxide nor lithium hydroxide should be used where sodium carbonate and/ or potassium carbonate are used); (c) forming a third mixture by maintaining the second mixture at about 40-90" C. (preferably about 60-70 C.) for about 30-240 minutes (preferably about 60-120 minutes); and (d) forming the AAC by adjusting the pH of the third mixture to about 6.5-7 (e.g., by adding an acid such as sulfuric acid, acetic acid, formic acid, hydrochloric acid, phosphoric acid, or the like). Typical of the aminoplast precursors which have been used with excellent results to prepare this composition include melamine, urea, ethylene urea, dihydroxyethyleneurea, propyleneurea, and mixtures of two or more such aminoplast precursors.

In preferred embodiments of the AAC set forth in Embodiment G, supra:

(l) x is R is CH and R R R and R are hydrogen.

(2) x is 0; R is CH R is hydrogen; R is SO R is H; and R is H or -CH OH.

(3) x is 0; R is CH R R and R are hydrogen; and R is -CH OH.

This invention is also directed to:

(l) A composition consisting essentially of a cellulosic textile material wetted with about 10-60% of the composition of Embodiment G, supra.

(2) A composition consisting essentially of a cellulosic textile material wetted with about 10-60% of the composition of Embodiment G, supra, and dried.

3) A composition consisting essentially of a cellulosic textile material wetted with about 10-60% of the composition of Embodiment G, supra, dried, and cured, e.g., by radiation or by heating in the presence of a gaseous acidic I curing catalyst such as S0 HCl, formic acid vapor, HBr,

and the like.

In another preferred embodiment (Embodiment H) this invention is directed to an aqueous aminoplast creaseproofing agent (ACA) prepared by admixing the composition of Embodiment G, supra, and an effective quantity of an acidic curing catalyst.

In preferred embodiments of the ACA of Embodiment H, supra:

(l) x is 0; R is CH and R R R and R are hydrogen.

(2) x is 0; R is CH R is hydrogen; R is 50 R is H; and R is H or CH -OH.

(3) x is 0; R is -CH R R and R are hydrogen; and R is --CH OH.

This invention is also directed to:

(l) A composition consisting essentially of a cellulosic textile material wetted with about 10-60% of the ACA of Embodiment H, supra.

(2) A composition consisting essentially of a cellulosic textile material wetted with about 10-60% of the ACA of Embodiment H, supra, and dried.

(3) A composition consisting essentially of a cellulosic I textile material Wetted with about 10-60% of the ACA of Embodiment H, supra, dried, and cured, e.g., by heating or by irradiating.

In another preferred embodiment (Embodiment I) the process of Embodiment D, supra, and the embodiments thereunder has been conducted with excellent results using the AAC of Embodiment G, supra, and the embodiments thereunder.

In another preferred embodiment (Embodiment I) the process of Embodiment C, supra, and the embodiments thereunder has been conducted with excellent results using the ACA of Embodiment H, supra, and the embodiments thereunder.

In another preferred embodiment (Embodiment la) the process of Embodiment F, supra, and the embodiments thereunder has been conducted with excellent results using the ACA of Embodiment H, supra, and the embodiments thereunder.

We have found (Embodiment K) that the quality of paper (especially its wet strength, Wet abrasion resistance, wet tensile strength, wet tear strength, and water absorption characteristics) can be greatly improved by impregnating the paper with an improved AAC of our invention, drying the impregnated paper, and curing the dried impregnated paper by irradiation or by heating. Where using an AAC for this purpose it is often called an aqueous aminoplast paper treating compositiona terminol ogy which we sometimes use.

We have also found (Embodiment L) that the quality of paper (especially its wet strength, abrasion resistance, wet tensile strength, and wet tear strength) can be greatly improved by impregnating the paper with an improved ACA of our invention, drying the impregnated paper and curing the dried impregnated paper by heating-the improved ACA containing about 0.1-5% of an acidic catalyst. Where using an ACA for this purpose it is often called an aqueous aminoplast paper treating agenta terminology which we often use.

We have also found (Embodiment M) that the general methods (or procedures) of Embodiment E, supra, and the embodiments thereunder can be used to improve the physical property of paper (especially its wet strength, wet abrasion resistance, wet tensile strength, and wet tear strength). Paper treated with the improved AACs and ACAs of our invention is useful as paper toweling, high wet strength absorbtive paper, filter paper, and the like.

In another preferred embodiment (Embodiment N) this invention is directed to an improvement in a process for treating a cellulosic textile material with an aqueous aminoplast composition comprising impregnating the cellulosic textile material with the aqueous aminoplast composition and drying the impregnated cellulosic textile material, the improvement comprising incorporating into the aqueous aminoplast composition an effective amount of a member selected from a first group consisting of;

Where (a) x is or 1;

(b) R is hydrogen or an alkyl group having about 1-5 carbon atoms;

(c) R is hydrogen or an alkyl group having about 1-5 carbon atoms;

(d) R is hydrogen, an alkyl group having about 1-5 carbon atoms, or -SO' (e) R; is hydrogen, an alkyl group having about 1-8 carbon atoms,

(f) R is hydrogen, an alkyl group having about 1-8 carbon atoms,

CH2CH2OH; or OH2OH;

and

(g) A is a member selected from a second group consisting of;

N CH2; CHnCflg ii Gri -0H,

cH Cz and (iii) G L- H2 CHzC Hz lIn preferred embodiments of the process set forth in Embodiment N, supra:

x iS R1 is and R2, R3, R4, and. R5 are hydrogen.

(2) x is 0; R is -CH R is hydrogen; R is SO;,*; R is H; and R is H or CH OH.

(3) x is 0; R is CH R R and R are hydrogen; and R is CH OH.

In another preferred embodiment (Embodiment 0) this invention is directed to an improvement in a process for treating a cellulosic textile material with an aqueous aminoplast creaseproofing agent, the process comprising impregnating the cellulosic textile material with the aqueous aminoplast creaseproofing agent and drying the impregnated cellulosic textile material, the improvement comprising admixing the aqueous aminoplast creaseproofing agent with an effective amount of a member selected from a first group consisting of;

Where; i t

(a) x is 0 or 1;

(b) R is hydrogen or an alkyl group having about 1-5 carbon atoms;

(c) R is hydrogen or an alkyl group having about 1-5 carbon atoms;

(d) R is hydrogen, an alkyl group having about 1-5 carbon atoms, -SO

14 (e) R; is hydrogen, an alkyl group having about 1-8 carbon atoms,

(f) R is hydrogen, an alkyl group having about 1-8 carbon atoms,

(g) A is a member selected from a second group consisting of;

In preferred embodiments of the process of Embodiment O, supra:

(1) x is 0; R is -CH and R R R and R are hydrogen.

(2) x is 0; R is CH R is hydrogen; R is -SO;,; R is H; and R is -CH OH.

(3) x is 0; R is CH R R and R are hydrogen; and R is CH OH.

In another preferred embodiment (Embodiment P) this invention is directed to a process for treating a cellulosic textile material with a member of a later recited first group to improve the physical properties of said cellulosic textile material comprising impregnating the cellulosic textile material with a sufficient quantity of an aqueous solution of a member selected from said first group to provide an effective amount of the first group member, said first group consisting of;

bon atoms,

CHiCH1OH; or

(f) R is hydrogen, an alkyl group having about 1-8 carbon atoms,

(g) A is a member selected from a second group consisting of;

( CHi-CH7 CHr-CH:

and drying the impregnated ceilulosic textile material.

In preferred embodiments of the process of Embodiment P, supra:

(1) x is R is CH and R R R and R are hydrogen.

(2) x is 0; R is CH;,; R is hydrogen; R is SO R is H; and R is H or -CH OH.

(3) x is 0; R is CH R R and R are hydrogen; and R is -CH OH.

In another preferred embodiment (Embodiment Q) this invention is directed to an improvement in a process for treating a cellulosic textile material with an aqueous aminoplast composition comprising impregnating the cellulosic textile material with an aqueous aminoplast composition and drying the impregnated cellulosic textile material, the improvement comprising; preparing the aqueous aminoplast composition by; (a) forming a first mixture by admixing an aminoplast precursor, aqueous formaldehyde, and an efiective amount of a member selected from a group consisting of;

R1 r a r r R (E GHz C-N ;and R1CLGH2\ C-A A a A B5 0 R: H

where;

'bon atoms,

-ornon,on; or @z (vi) R is hydrogen, an alkyl group having about 1-8 carbon atoms,

(vii) A is a member selected from a second group consisting of;

and

the equivalent ratio of aminoplast precursor to formaldehyde being about 1:1.1-2; (b) forming a second mixture by adjusting the pH of the first mixture to about 8.5-10.5; (0) forming a third mixture by maintaining the second mixture at about 40-90 C. for about 30-240 minutes; and (d) forming the aqueous aminoplast composition by adjusting the pH of the third mixture to about 6.5-7.

In preferred embodiments of the process of Embodiment Q, supra:

(1) x is 0; R is CH and R R R and R are hydrogen.

(2) x is 0; R is CH;,; R is hydrogen; R is 40 R is H; and R is H or --CH OH.

(3) x is 0; R is CH R R and R are hydrogen; and R5 IS CH2OH.

In another preferred embodiment (Embodiment R) this invention is directed to an improvement in a process for treating a cellulosic textile material with an aminoplast creaseproofing agent comprising impregnating the cellulosic textile material with an aqueous aminoplast creaseproofing agent and drying the impregnated cellulosic textile material, the improvement comprising; preparing the aqueous aminoplast creaseproofing agent by; (a) forming a first mixture by admixing an aminoplast precursor, aqueous formaldehyde, and an effective amount of a member selected from a group consisting of;

(vi) R is hydrogen, an allryl group having about 1-8 carbon atoms,

431120112011; 0 or -ornoH;

(vii) A is a member selected from a second group consisting of;

and

O and CHICH1 CH -CH;

the equivalent ratio of aminoplast precursor to formaldehyde being about 1:1.1-2; (b) forming a second mixture by adjusting the pH of the first mixture to about -105; (0) forming a third mixture by maintaining the second mixture at about 40-90 C. for about 30-240 minutes; (d) forming the aqueous aminoplast composition by adjusting the pH of the third mixture to about 6.5-7, and (e) admixing the aqueous aminoplast composition with an etfective amount of an acidic curing catalyst.

In preferred embodiments of the process of Embodiment R, supra:

(1) x is 0; R is -CH;,; and R R R and R are hydrogen.

(2) x is 0; R is -CH R is hydrogen; R is SO R is H; and R is H or -CH OH.

(3) x is 0; R is -CH R R and R are hydrogen; and R is CH OH.

In another preferred embodiment (Embodiment S) this invention is directed to a process for treating cellulosic paper with a member of a later recited first group 17 to improve the physical properties of the cellulosic paper comprising; impregnating the cellulosic paper with a sufficient quantity of an aqueous solution of a member selected from a later recited first group to provide an effective amount of the first group member, said first group consisting of;

where;

(a) x is or 1;

(b) R is hydrogen or an alkyl group having about lcarbon atoms;

(c) R is hydrogen or an alkyl group having about 1-5 carbon atoms;

(d) R is hydrogen, an alkyl group having about 1-5 carbon atoms, or SO (e) R, is hydrogen, an alkyl group having about 1-8 carbon atoms,

(f) R is hydrogen, an alkyl group having about 1-8 carbon atoms,

-cnicmon;; or -crr.0H; and

(g) A is a member selected from a second group consisting of;

( CHI-CH3 GHQ-O 2 \CHPCQI and ( GHQ-CH2 CHaC Hz and drying the impregnated cellulosic paper.

In preferred embodiments of the process of Embodiments S, supra:

(1) x is 0; R is -CH and R R R and R are hydrogen.

(2) x is 0; R is CH R is hydrogen; R is SO;;; R is H; and R is H or CH OH.

(3) x is 0; R is CH R R and R are hydrogen; and R is CH OH.

In another preferred embodiment (Embodiment T) this invention is directed to an aqueous aminoplast composition (AAC) prepared by a process comprising; (a) forming a cfirst mixture by admixing an aminoplast precursor, water, amonia, and an effective amount of a compound having the formula (i) x is 0 to 1;

(ii) R is hydrogen or an alkyl group having about 1-5 carbon atoms;

(iii) R is hydrogen or an alkyl group having about 1-5 carbon atoms;

(iv) R is an alkyl group having about 1-5 carbon atoms,

the mole ratio of said compound to ammonia being about 1:1-10 (preferably about 1:2-5); (b) forming a second mixture by maintaining the first mixture at about 20100 C. (preferably about 4-6 hours); (c) forming a third mixture by removing (e.g. stripping or evaporated) unreacted ammonia from the second mixture e.g., by boiling; or by the application of heat and reduced pressure to induce vigorous boiling; or by the application of heat while purging with an inert gas (e.g., nitrogen, argon, helium, or the like) introduced into the second mixture via a sparger); (d) forming a fourth mixture by admixing aqueous formaldehyde with the third mixture, the equivalent ratio of aminoplast precursor to formaldehyde in the fourth mixture being about 1: 1.12 (preferably about 1:1.25-1.75); (e) form-ing fifth mix ture by adjusting the pH of the fourth mixture to about 8.510.5; (f) forming a sixth mixture by maintaining the fifth mixture at about 25-190 C., preferably about -180 C. (e.g., in a closed (pressurized) reaction zone) for about 0.25-4 hours (preferably about 1.5-3 hours); and (g) forming the aqueous aminoplast composition by adjusting the pH of the sixth mixture to about 6.5-7.

In another preferred embodiment this invention is directed to the AAC of Embodiment T, supra, in which x is 0; R and R are CH and R is hydrogen.

In another preferred embodiment (Embodiment U) this invention is directed to an aqueous aminoplast creaseproofing agent (ACA) prepared by admixing the composition (AAC) of Embodiment T, supra, and an effective amount (or quantity) of an acidic curing catalyst.

In another preferred embodiment this invention is directed to the ACA of Embodiment U, supra, in which x is 0; R and R are CH and R is hydrogen.

The AAC of Embodiment T (and the preferred embodiment thereunder) has been used with excellent results in the process of Embodiments I, Q, and K.

The ACA of Embodiment U (and the preferred embodiment thereunder) has been used with excellent results in the process of Embodiments J, Ia, R, and K.

Where an AAC is used to treat cellulosic paper it (the AAC) has been called an Aqueous Aminoplast Paper Treating Composition, and where an ACA is used to treat cellulosic paper it (the ACA) has been called an Aqueous Aminoplast Paper Treating Agent.

DETAILED DESCRIPTION OF THE INVENTION There is an ever increasing demand for easy care, permanent press, creaseproof, and durable press garments and fabrics, that is, for garments and fabrics which have creases and pleats durably pressed into them and which remain substantially wrinkle-free in normal wear or use and which can be used after washing without requiring much, if any, repressing. These include the so-called wash-and-wear garments. As is well 'known, such durable press and permanent press garments and fabrics can be otbained by applying to and curing on the textile material one or more of a wide variety of heat curable aminoplasts (also known as curable durable press textile resins (U.S. Pat. No. 3,527,558, Tomasino et al., 8/ 116.2)). These are aminoplasts which can be cured on the fabric by impregnating the fabric with an aqueous solution of the aminoplast, said solution also containing an acidic catalyst such as zinc nitrate, magnesium chloride, or the like, drying, and heating, or irradiating (e.g., exposure to radiation such as infrared, ultarviolet, X- rays, gamma rays, an electron beam, a proton beam, or a neutron beam), or by the application of vacuum plus heat. Where using vacuum and heat the temperature is just sufiicient to cure the aminoplast after volatile materials (e.g., H 0 and HCHO) are removed.

In one embodiment which is called precuring the drying and curing step is conducted as a continuous operation having the temperature in the drying stage below the curing temperature of the aminoplast. The drying stage is followed by a curing stage in which the dried impregnated fabric is heated to a temperature at which the aminoplast is cured, or the drying stage can be followed by irradiation.

Aminoplasts (curable durable press and permanent press textile resins) excellently adapted for use in aminoplast crease proofing agents and the preparation and use of these creaseproofing agents is well known to those skilled in the art. An aminoplast is generally applied to cellulosic textile materials as an aqueous aminoplast creaseproofing agent (ACA) comprising an aqueous solution or suspension. The aminoplast per se and the acidic catalyst component of the aminoplast creaseproofing agent are generally soluble in water but the ACA can also contain wetting agents, softeners, brighteners, chelating agents, and the like, some of which can be only slightly soluble (or substantially insoluble) in Water resulting in the presence of an insoluble phase being present in the ACA. In other words, the ACA is a dispersion when an insoluble phase is present.

In general, the ACA is applied to a cellulosic textile material and dried (by the application of heat (maintaining the temperature below the curing temperature) and/or vacuum) to about the normal moisture content of the textile material under ordinary room conditions (e.g., ca. 11530 C., and ca. 15-90% relative humidity). The thus dried textile material is then processed; (a) if the cellulosic textile material is fiber, it is spun and woven or formed into cloth or fabric, or formed into a nonwoven cellulose containing fabric like material, pressed, and cured before or after being woven into thread or before or after being formed into cloth, fabric, or nonwoven cellulosic-containing fabric like material. Alternatively, the dried fiber can be formed into a non-woven fabric and cured before or after being processed into a garment, sheet, tablecloth, or the like; (b) if thread, it is woven or formed into cloth or fabric, pressed and cured before or after being processed into a garment; and (c) if cloth or fabric, it can be (i) pressed free of wrinkles and cured; or (ii) processed into an article of clothing, pressed, and cured. Subsequent to curing the cloth or garment can be washed to remove any uncured aminoplast remaining thereon and other components of the arninoplast creaseproofing agent (e.g., catalyst) which are removable by washing. Alternatively, a garment can be impregnated with an aminoplast creaseproofing agent,

dried, pressed, and cured.

Wegenerally prefer to bleach and scour a cellulosic textile material before treating it with the ACA or AAC to which we have added a member of the first group of the above summary.

Typical aminoplasts which are used in aminoplast crease-proofing agents and/or typical acidic catalysts which are used in aminoplast creaseproofing agents to catalyze the curing of the aminoplast component of such agents, and typical methods of using aminoplast creaseproofing agents are taught by the following US. patents which are incorporated herein by reference:

2,974,432 (Warnock et al., 38/ 144) 3,138,802 (Getchell, 2/243) 2,357,273 (Thurston, 260/ 29) 3,181,927 (Roth et al., 8/116.3) 2,887,409 (Van Loo, 117/ 139.4) 3,450,485 (Reinhardt et al., 8/ 116.3) 3,144,299 (Frick et al., 8/1l6.3) 3,391,181 (Scheurel, 260/482) 3,527,558 (Tomassino et al., 8/ 116.2) 3,531,806 (Shore, 2/243).

Preferred aminoplasts include diand poly-N-methyol, N-methoxymethyl, and N-lower alkoxymethyl derivatives of urea, cyclic ethylene urea, alkyltriazones, cyclic propylene urea, 4,5-dihydroxy cyclic ethylene urea, dimethylol alkyl carbamates, triazines, uron, and thiourea. Preferred aminoplast also include dimethylol propylene urea; dimethylol ethylene urea; polymethylol melamine; formaldehyde-imidazolidinone adducts; mixtures of dimethylol imidazolidinone-Z and its water-soluble ethers; methylol derivatives of 4,5 dihydroxyimidazolidone, 1,3 di methyl 4,5 dihydroxy 2 imidazolidinone, and alkyl substituted 4,5 dihydroxy 2 imidazolidinones; reaction product of dimethylol dihydroxyethylene urea and p-dioxane; 1,3 dimethylol 4,5 bis(alkoxy) 2 imidazolidinones; 1,3 bis(hydroxymethyl) 2 imidazolidone; imidazolidinone-aminoplast blends; reaction products of urea, glyoxal and formaldehyde; polyalkylated monoureins; alkylated uron resin admixed with melamine formaldehyde compositions; N,N'-dimethyloluron dialkyl ether and urea-formaldehyde compositions; alkyl-ated uron resin and triazone compositions; amine-modified uron resins; N,N'-bis(acyloxymethyl) urons; N,N'-bis(methoxymethyl) urea-formaldehyde addition products; N,N- bis(methoxymethyl) man-formaldehyde addition and reaction products; urea-formaldehyde condensation products; dicyandiamide-urea-formaldehyde agents; combination of monomeric and polymeric urea-formaldehyde condensates; 2-hydroxyethylamine-urca-formaldehyde condensation products; amine modified cyclic urea resins; polymethylol ureas having a high formaldehydemrea ratio, aminoethanol-urea-formaldehyde reaction product; highly alkylolated nitrogen compounds; and diketone dialdehyde-cyclic amide condensation products.

Aminoplast precursors are well known to those skilled in the art. Said precursors are amine type compounds (including amides) which can be reacted with formaldehyde in basic or slightly acidic systems to form a material which forms an aqueous aminoplast composition when the pH is adjusted to about neutral (e.g., to about 6.5-7).

Among the many aminoplast precursors which have been used with excellent results are urea, biuret, melamine, and other triazines, ethylene urea, propylene urea, alkyl carbonates, thiourea, 4,5 dihydroxyimidazolidone, 1,3- dimethyl 4,5 dihydroxy 2 imidazolidone; alkyl substituted 4,5 dihydroxy 2 imidazolidinones; alkyl carbarnates; triazine resins; and the like.

Preferred acidic curing catalysts include zirconium acetate, aluminum acetate, lead acetate, manganese acetate, cupric acetate, zinc acetate, zinc nitrate, magnesium chloride, mixtures of zinc and aluminum nitrates, zinc fluoborate, zinc perchlorate, zinc chloride, magnesium chloride, mixtures of magnesium chloride and formic acid, mixtures of magnesium chloride and citric acid, sulfonic acid salts of ammonia, phosphoric acid salts of ammonia, volatile (e.g., gaseous) acids such as HCl, HBr, S0 and the like.

In another embodiment which i fully equivalent, an aqueous aminoplast composition (AAC), which can contain a brightener, a softener, a wetting agent, a chelating agent, and the like, is prepared, but the acidic catalyst is omitted where preparing the AAC. Where using the AAC, 9. cellulosic textile material is impregnated with the AAC, dried, and cured by heating to the arninoplasts curing temperature in the presence of an acidic gas such as HCl, HBr, 50:, or the like. Alternatively, the dried impregnated cellulosic textile material can be irradiated (e.g., with infrared, ultraviolet, X-rays, gamma rays, an electron beam, and the like) to cure the aminoplast. Excellent results have been obtained where an effective quantity of one or more of the aforesaid first group members was incorporated into the aqueous aminoplast composition before impregnating the cellulosic textile material with the aqueous aminoplast composition.

While the concentration of aminoplast and acidic catalyst in an ACA and the concentration of aminoplast in an AAC used in this invention are not critical, we generally prefer the aminoplast creaseproofing agent (solution or dispersion) as applied to cellulosic textile material (i.e., the aminoplast plus water (and any water soluble solvent) plus first group member, plus (in the instant of an ACA) acidic curing catalyst, plus brighteners, softeners, chelating agents, and the like) to contain about 25-50% or higher (or about 530%) of said aminoplast and (in the instance of an ACA) about 0.2510% (or about 0.56%) of said acidic catalyst (acidic curing catalyst). As noted supra, the acidic catalyst can be omitted, thereby to form an aqueous aminoplast composition (AAC) rather than the ACA. The aminoplast of the aqueous aminoplast composition is cured by; (a) irradiating; or (b) heating in the presence of an acidic gas. An effective amount of aminoplast must be present in any ACA or AAC and an effective amount of acidic catalyst must be present in any ACA.

Typical of the wetting agents which can be used with excellent results are sodium lauryl sulfate, dioctyl sodium sulfosuccinate, sodium lauroyl sarcosinate, alkyl phenolpolyoxyethylene glycols, sodium or potassium salts of high molecular weight alkyl sulfates, sodium or potassium salts of high molecular weight alkyl sulfonates, and the like.

Typical chelating agents which can be used with excellent results are sodium or potassium ethylenediaminetetraacetate, sodium or potassium nitrilotriacetate, sodium B-hydroxyethylethylenediaminetriacetate, and the like.

Typical of the brighteners which can be used with excellent results are bistriazinyl derivatives of 4,4-diaminostilbene 2,2 disulfonic acid, naphthotriazolylstilbene sulfonic acid derivatives, and the like.

Typical of the additives and softening agents which can be used with excellent results are polyethylene emulsions, acrylic emulsions, silicones, wax emulsions, fiuorocarbons, and chromium salts of higher fatty acids, sulfonated oils, sulfated fatty alcohols, quaternary ammonium salts, and the like.

The quantities of wetting agent, brightener, softener, and chelating agent are not critical to the instant invention; however, for economic reasons where one or more of these is used each is generally present in an effective amount.

We can prepare the improved ACA described in our above summary by admixing an effective quantity of a member of the aforesaid first group (the first group of the above summary) and an ACA solution or dispersion. Where the first group member is a methylol compound having the formula (where x, R R R and R are as recited in the above summary) we can prepare the methylol compound by reacting a compound (Compound A) having the formula (Compound A) with aqueous formaldehyde in the presence of a base (e.g., Ba(H) and adding the resulting methylol compound to the ACA. Alternatively, a methlyol compound can be formed in situ by adding the Compound A to an ACA or to an AAC which contains excess HC-HO'. If the Compound A is added to an AAC the pH of the AAC should preferably be above 7 and preferably about 8.5- 9.5; where forming the methylol compound in the AAC. (However, an acidic pH (e.g., generally about 5.0-6.9 or 5.5-6.5) is used where the aminoplast is dimethyloldihydroxyethyleneurea.) Subsequent to forming the methylol compound in situ in an AAC containing excess formaldehyde, we can adjust the pH to about 6.5-7 (if pH adjustment is required) and add an acidic catalyst to conwert the AAC to an ACA. Said ACA will, when formed, contain a methylol compound derived from Compound A.

We prepare the improved AAC of our Embodiment A, supra by admixing an effective quantity of a member selected from the first group recited in said Embodiment 22 A and an AAC solution or dispersion. Where the first group member is a methylol compound having the formula' (where 2:, R R R and R are as recited in said Embodiment A) we can prepare said methylol compound by reacting the above described Compound A with aqueous formaldehyde in the presence of a base and add the resulting methylol compound to the AAC. Alternatively, the methylol compound can be formed in situ by adding Compound A to an AAC which contains an excess of formaldehyde, thereby forming the composition recited in Embodiment A wherein the first group member is a methylol compound recited in said first group.

We have found that the concentration of first group member present in the ACAs of our invention or the AACs of our invention can be varied over wide limits and still produce excellent and effective results. However, we generally prefer that the concentration of said first group member be about 05-35% (or about 2-10%) based on the weight of the resulting composition (the ACA or AAC as applied to a cellulosic textile material, i.e., the ACA or AAC plus said first group member (the first group of the summary or Embodiment H in the instance of an ACA and the first group of Embodiment A or G in the instance of an AAC) plus any water (and other solvent) added with said first group member).

Excellent results have been obtained where said compositions contain concentrations of said first group member much higher than about 35%, but no technical advantage is obtained by using first group member concentrations greater than about 25% and the use of first group member concentrations higher than about 25% is economically unattractive. Said compositions in which the concentration of the first group member is significantly lower than the aforesaid about 0.5% produce beneficial results, but the hand, abrasion resistance, tensile strength, tear resistance, and shrinkage obtained at these low first group members concentrations are, in some instance, somewhat less desirable than where the first group members concentration is about 0.5% or higher. Because of our disclosure one skilled in the art can readily determine the concentration of said first group member which will give optimum results in a given ACA or AAC where said ACA or AAC is used for a particular purpose with a specific cellulosic textile material (e.g., to prepare washand-wear or permanent press shirts from cotton cloth or from a blend of cotton and polyester).

N-methylollactamide,

is a well known compound having been prepared by Einhorn et al. -(Ann., 1908, 361, 113; Beilstein, 1921, III, 283; C.A., 1908, 2, 2682) by reacting lactamide and formaldehyde solution in the presence of baryta (Ba(OH) The other N-methylol compounds recited in the first group of our above summary and our above preferred embodiments can be prepared by the general method of Einhorn et a1. wherein lactamide is replaced by the appropriate amide having a hydrogen on the amide nitrogen. We prefer to perpare lactamide for use in our invention by the general procedure set forth infra.

We have found that incorporating one or more of our first group members into an ACA or AAC does not require any substantial change in the apparatus, or method, or conditions (temperature, time, and the like) used to apply the ACA or AAC to a cellulosic textile material and to dry and cure the aminoplast component of the ACA or AAC where said ACA or AAC is applied to said textile material (or to cellulosie paper). In other words, the same general apparatus, method, and conditions used to apply a given ACA or AAC to a given cellulosic textile material (or to cellulosic paper) and to cure the aminoplast component of said ACA or AAC on said textile material (or paper) can be used to apply, dry, and cure said ACA or AAC after an etfective amount of one or more of our first group members has been admixed with said ACA or AAC (to make the ACA or AAC-an improved ACA or AAC of our invention).

As is well known to those skilled in the art some aqueous aminoplast creaseproofing agents (ACAs) require the addition of an acid such as acetic acid, sulfuric acid, formic acid, phosphoric acid, or the like to reduce the pH of the ACA before the ACA can be cured by the application of heat or heat and vacuum. Where using such an ACA in our invention, we add thereto a quantity of acid effective to render the ACA heat curable. This technique is well known in the prior art, and incorporating additives such as those of the above summary or the above Embodiment H into an ACA does not significantly change the technique.

Claims directed to compositions and processes of the instant invention recite an effective amount (or an effective quantity) of a member of a first group (e.g., the first group of the above summary or the first group of Embodiments A, B, C, D, E, F, G, or H); however, because of our disclosure, it is readily apparent to those skilled in the art that an elfective amount of first group members can be obtained by admixing two or more of the members of said first group even though the amount of any one individual group member in the resulting mixture is not suflicient if taken alone to constitute an elfective amount.

More than an effective amount of said group member (or a combination of more than 1 member of said group to total more than an efiective amount) can be present in the compositions or processes of this invention, but, in general, little or no advantage is gained by using more than an effective amount, and cost of said group member (or members) tends to render the use of more than at least about an effective amount economically unattractive.

Claims directed to the compositions and processes of the instant invention recite an aqueous aminoplast composition, an aqueous aminoplast creaseproofing agen an aqueous aminoplast paper treating composition, or an aqueous aminoplast paper treating agent; however, it will, because of our disclosure, be readily apparent to those skilled in the art that each of the aqueous aminoplast compositions or aqueous aminoplast agents can; (a) contain at least one aminoplast (i.e., each aqueous aminoplast composition or agent can contain 1, or 2, or more aminoplasts); and (h) each aqueous aminoplast composition can contain up to about -20% or more of a non-aqueous solvent (or a mixture of two or more non-aqueous solvents) said non-aqueous solvent (or solvents) being soluble in water. Typical examples of nonaqueous solvents excellently adapted for inclusion in our aqueous compositions and agents are methyl alcohol, dimethylformamide, dimethyl sulfoxide, isopropyl alcohol, ethyl alcohol, and the like.

Likewise, because of our disclosure, it will be readily apparent to those skilled in the art that an aqueous solution of a member of a first group such as the aqueous solution of Embodiment E, supra, can contain up to about 20% or more of non-aqueous solvent (or a mixture of two or more non-aqueous solvents) said non-aqueous solvent (solvents) being soluble in water. Typical examples of non-aqueous solvents excellently adapted for inclusion in an aqueous solution such as that of Embodiment E, supra, include ethyl alcohol, isopropyl alcohol, methyl alcohol, dimethyl sulfoxide, dimethylformamide, and the like.

If desired, a cellulosic textile material can be impreg nated with an ACA or AAC of our invention, dried, and

24- placed in storage or shipped to a processing plant before being cured. Shelf life is generally at least about 3 months. Fabric which has been impregnated with an ACA or AAC and dried but not cured can be rolled and shipped or stored as a fabric roll.

If desired, a cellulosic textile material can be impregnated with an aqueous system comprising a member of the first group of the above summary, dried, and placed in storage or shipped before being cured with an aldehyde. Shelf life is about 6 months. Fabric which has been impregnated with said group member and dried but not cured with aldehyde can be formed into a bolt or roll before being shipped or stored.

It is well known to those skilled in the art that where one treats a cellulosic textile material with an ACA or an AAC he applied a quantity of the ACA or AAC sufiicient to provide an effective amount (an effective quantity) of the aminoplast component of the ACA or AAC to the cellulosic textile material. When using an ACA or an AAC of our invention we apply an amount sufficient to provide an effective amount of the aminoplast component of said ACA or AAC.

It is also well known to those skilled in the art that where one treats a cellulosic paper with an aqueous aminoplast paper treating agent or an aqueous aminoplast paper treating composition he applies a quantity of said agent or said composition sufiicient to provide an effective amount (an effective quantity) of the aminoplast component (or components) of said agent or said composition to the cellulosic paper. Where using a paper treating agent or a paper treating composition of our invention we apply an amount sufiicient to provide an effective amount of the aminoplast component of said agent or composition.

As is well known in the art, where one cures a cellulosic textile material which has been impregnated with an AAC and dried by heating the dried impregnated cellulosic material in the presence of an acid (e.g., gaseous HCl, HBr, S0 formic acid vapor and the like) he has an effective amount of the acid present.

As is also well known in the art, where one cures a cellulosic paper which has been impregnated with an aqueous aminoplast paper treating composition and dried by heating the dried impregnated paper in the presence of an acid (e.g., gaseous HCl, HBr, S0 formic acid vapor, and the like) he has an elfective amount of the acid present.

The instant invention will be better understood by referring to the following specific but nonlimiting examples. It is understood that said invention is not limited by these examples which are offered merely as illustratrons; it is also understood that modifications can be made without departing from the spirit and scope of the invention.

EXAMPLE 1 Lactamide was prepared from methyl lactate by the following procedure:

To 1 mole of freshly distilled methyl lactate was added about 2 moles of ammonia. The ammonia was added as an aqueous solution analyzing about 28% NH;,. The resulting mixture was agitated for about 3 hours at about 2 0-30 C. Then full vacuum from a water pump (aspiratron type filter pump) was applied to the mixture which was heated to about 70 C. to remove water and unreactcd ammonia. Purity of product was about 91% and conversion (one pass yield) was about 97% of theory. The same general procedure was used to prepare amides of glycolic acid, B-hydroxypropionic acid, p-methoxypropionic acid, a-methoxypropionic acid, a-normal-butoxypropionic acid, methoxyacetic acid, ethoxyacetic acid, Ot-lSO-PIOPOXYPI'OPiOHlC acid, and other organic acids of the type required to form the amides set forth in the above summary. In each instance a high quality product was obtained in excellent yield.

Methyl m-methoxypropionate (part of which was used to prepare the amide of ut-methoxypropionic acid) was prepared by reacting methyl lactate with metallic sodium to form the sodium alkoxide which was converted to methyl a-methoxypropionate by reaction with methyl iodide. Methyl a-normal-butoxypropionate (part of which was used to prepare the amide of a-normal-butoxypropionic acid) was prepared in a similar manner by replacing the methyl iodide with n-butyl iodide. Methyl B- methoxypropionate (part of which was used to prepare the amide of S-methoxypropionic acid) was prepared in was obtained when the methylamine was replaced with monoethanolamine, and

(R CHzCHzOH CHaC- -N H CHzCHgOH was obtained when the methylamine was replaced with diethanolamine.

Table I shows some of the substituted amides which were prepared by the above general method.

a. similar manner from fi-hydroxypropionate. Methyl ethoxyacetate (part of which was used to prepare the amide of ethoxyacetic acid) was prepared in a similar manner using methyl glycolate and ethyl iodide as starting materials. Methyl a-iso-propoxypropionate (part of which was used to prepare the amide of a-iSO-PIOPOXY- propionic acid) was prepared in a similar manner from methyl lactate and iso-propyl iodide. Other methyl esters of alkoxy acids were prepared by the same general proeedure.

EXAMPLE 2 The general procedure of Example 1 was used to prepare of excellent quality with excellent conversion by reacting methyl lactate with methylamine.

O OH; I! CHaCH- N H CH3 was prepared by replacing the methylamine with dimethylamine, and

was obtained when the methylamine was replaced with methylethylamine.

CHaGH-(i-N H CHaCHgOH Compounds having the general formula where R R 1:, and A are as defined in the above summary, were prepared by the general method of Example 2 except that the methylamine of Example 2 was replaced with piperidine, where A was CHz-C a morpholine, where A was GHQ-CH] CHzC 2 and pyrrolidine, where A was CH5CH3 CHgCHa.

Among the compounds of excellent quality prepared in good to excellent conversion were those resulting from the reaction of piperidine, morpholine, and pyrrolid ine, respectively, 'with methyl lactate, methyl p-hydroxypropionate, methyl glycolate,

OH, (I? cHr-i lcmcocmz and O (llHzCHzCI-Iz -OCHQ, 0 H respectively.

27 EXAMPLE 4 was prepared by heating aniline with a large excess of lactic acid for about an hour at about 105 C. in a flask provided with a fractionating column for removing by-product water, cooling the resulting reacted mixture and diluting it with a large volume of ice water to precipitate the anilide which was separated by filtration, washed with water, and air dried. An excellent product was obtained with a conversion in excess of about 75% of theory where using a mole ratio of lactic acid to aniline of about :1 and where the anilide was precipitated by pouring the cooled reacted mixture into a large volume of ice water (ca. volumes of ice water per volume of reacted mixture).

The above general procedure was used to prepare anilides of a large number of hydroxy and alkoxy acids including anilides of; a-methoxypropionic acid, a-ethoxypropionic acid, glycolic acid, methoxyglycolic acid, B-methoxypropionic acid, B-isopropoxypropionic acid, and ahydroxybutyric acid. In each instance an anilide of excellent quality was obtained in excellent yield.

EXAMPLE 5 The general method of Example 4 was used to prepare CHaCHii-N by replacing the aniline of Example 3 with diphenylamine.

An excellent product was obtained with a conversion in excess of about 70% of theory.

The above general procedure was used to prepare a large number of compounds having the formula Among the compounds prepared were those in which the lactic acid of the above procedure was replaced with the following acids; a-methoxypropionic acid; p-methoxypropionic acid; a-n-butoxypropionic acid;

and

EXAMPLE 6 mixture to 10. Said resulting mixture was then heated to 60-70" C. for 2 hours (with stirring), cooled to about 25 C., and its pH was adjusted to 7 with sulfuric acid. The thus prepared mixture was filtered. The resulting filtrate (which was designated Solution No. 6) weighed 5151 grams and had a free HCHO content of 14.6%. A second 20 mole portion of the above-described lactamide was added to Solution No. 6 and the above-described procedure was repeated. In this instance the filtrate (which was designated Solution 6A) Weighed 6710 g. and contained 2% free HCHO and about 37 moles of N-rnethylollactamide.

A large number of other N-methylolamides of excellent quality were prepared in good to excellent yields by the general procedure of Einhorn but modified by replacing the lactamide of Einhorn with another amide. Table II lists some of the N-methylolamides prepared:

TABLE 2 Amide N-methylolamide D H ll ll ?H2 :\CNH1 (7HaCHaC-N\ O O C H: O H H H ll ll CH3GH:CNHI CHICHIC-N O CHQOH C H; O CH;

ll ll CHaCHCf-NH: CHaGHC-N O C HnOH 02H; CzHl i CH:(l3HC-N\ CHaCHC-N O H A CHzOH CH CH;

(6 /C H! g) /C-Hg $111 CN\ ?H1CN\ O H 0 (3112011 H H 0 I: ll CHeCH NH1 CHttCHC-N S 04H SO4N2. 0112011 In preparing this compound the Ba(0H)g of Einhorn was replaced with NaOH. 0n acidification the Na is replaced with H.

EXAMPLE 7 The sulfate ester,

0 ll ll onions-NH, or emetic-N11,,

of excellent quality was prepared in excellent yield (conversion, one pass yield, of about of theory) by admixing one mole of lactonitrile (CI-I C(OH)HCN) and 200 ml. of dioxane and adding 98 g. of concentrated sulfuric acid thereto over a period of about 5 minutes. The resulting mixture was maintained at about 80-83 C. for about 4.5 hours. Some solid precipitated and was separated by filtration and recovered. The filtrate was poured into about ml. of dioxane.

The bottom oil-like layer contained substantially all of the remaining where R R and x are as above. Among the compounds formed were where R R R R and x are as defined supra (R being -SO is a sulfate ester of an amide of a hydroxy acid. The above ionic formula of said ester makes it readily apparent to those skilled in the art that: (a) where said sulfate ester is present in an acid medium, the negative valence shown on the SO moiety is satisfied by a hydrogen; and (b) where the sulfate ester is present in an alkaline or neutral medium, said negative valence is satisfied by a positive ion (or radical) other than hydogen, e.g., Na+, K NHJ, V2Ca++, or the like (i.e., said sulfate ester is present as a salt).

It is also readily apparent that such salt can hydrolyze to give acidic or neutral reactions depending on the relative ionization constants of the acid form of said ester,

and the free base (e.g., KOH or NH OH) which can be derived from the aforesaid positive ion (or radical).

30 EXAMPLE 8 Four aqueous solutions were prepared. These were:

Solution A: An aqueous dimehtyloldihydroxyethyleneurea (DMDHEU) solution having a 45% dissolved solid content. Said solution was prepared by reacting urea with glyoxal and methylolating the resulting product by reacting it with formaldehyde. Solution A had a free formaldehyde content of 7.1%.

Solution B: An aqueous N-methylollactamide (NML) solution having a dissolved solid content of 72%. It was prepared from lactamide and formaldehyde.

Solution C: An aqueous zinc nitrate solution having a dissolved solid content of 50%.

Solution D: An aqueous lactamide solution having a dissolved solid content of 70%.

A batch of ordinary ACA (not an improved ACA of our invention) was prepared by admixing an amount of Solution A to provide 30 parts of solid and an amount of Solution C to provide 6 parts of Zn(NO The resulting ACA was designated Solution 8A.

A batch of improved ACA (an ACA of our invention) was prepared by admixing an amount of Solution B to provide 5 parts of solid and one-fourth of the above-described Solution 8A (i.e., to that quantity of Solution 8A which was prepared from an amount of Solution A containing 7.5 parts of solid). The resulting improved ACA was designated Solution 8B.

Another batch of improved ACA (an ACA of our invention fully equivalent to the ACA designated Solution 8B, supra) was prepared by admixing a quantity of Solution A to provide 7.5 parts of solid and an amount of Solution B to provide 5 parts of solid. To the resulting mixture was added an amount of Solution C to provide 1.5 parts of Zn(NO The resulting improved ACA was designated Solution 80.

A batch of improved AAC (an AAC of our invention) was prepared by admixing an amount of Solution A to provide 30 parts of solid and an amount of Solution B to provide 20 parts of solid. The resulting improved AAC was designated Solution 8D. Another batch of improved ACA (an ACA of our invention fully equivalent to the ACAs designated Solution 8B and Solution 8C, supra) was prepared by admixing an amount of Solution C to provide 1.5 parts of Zn(NO and one-fourth of the above described Solution 8D (i.e., to that quantity of Solution 8D which was prepared from an amount of Solution A containing 7.5 parts of solid). The resulting improved ACA was designated Solution 8E.

Another batch of improved ACA (an ACA of our invention fully equivalent to the ACAs designated 8B, 8C, and 8D, supra) was prepared by adding a quantity of Solution D to provide 6 parts of lactamide to one-fourth of the above described Solution 8A. The resulting improved ACA was designated Solution 8F. I

The general procedure used to prepare Solution 8F, described supra, was repeated but in this instance said procedure was modified by replacing the Solution D with 4.6 parts by water and 10.7 parts of SO H The resulting solution was designated Solution 86.

EXAMPLE 9 Run No. 9A: A sample (ca. 76 cm. 'by 38 cm.) of 410W broadcloth combed lawn (a cellulosic broadcloth) was padded (ca. 81% Wet pickup) with Solution SA, described supra, after adjusting the dissolved solid content of said Solution 8A to 9% (by dilution with water). The padded sample was placed in a frame to maintain its size and shape, dried for 5 minutes at 93 C., and then cured for minutes at 163 C. The cured sample was labeled- Sample 9A.

Five additional runs were made using the general procedure described above but modified in each instance by replacing Solution 8A with the respective solution indicated in the following table, the dissolved solid content of each solution being adjusted to the concentration indicated by dilution with water before padding the cloth sample with the solution.

TABLE 3 Solid content of padding solution, percent;

Solution number Run number In this instance the general procedure oi Run 9A was further modified by conducting the curing step (5 minutes at 163 C.) in an atmosphere of sulfur dioxide.

EXAMPLE 10 Samples 9A and 98 were submitted to the tests listed in the following tables, and the results of these tests were as stated in said tables.

TABLE 4 weig ht of the padding solution was dried at 93 C. for 5 minutes. The thus dried corduroy was cut, pressed and cured (to simulate the fabrication of a garment from this material wherein it would be cut, sewed, pressed and cured). Pressing was carried out on a hot head press with a head temperature of 175 C. It was steamed for 30 seconds, vacuumed for 30 seconds without the head and with the blower turned oif, and baked at about 175 C. for 15 seconds under pressure. It was then cured at 160 C. for 5 minutes in an air circulating electric oven. A representative sample of the cellulosic corduroy cloth which had been treated according to the procedure of Run No. 11A designated Sample 11A.

Run No. 11B: The general procedure of Run No. 11A was repeated but in this instance, the cellulosic corduroy cloth (from the same lot as that used on Run No. 11A) was padded with Solution 11B. Solution 11B, an improved ACA of our invention, was prepared by admixing an amount of Solution B (Example 8) with Solution 11A to provide 5.3 parts of Solution B solids in the resulting Solution 11B. A representative sample of the cellulosic corduroy cloth which had been treated according to the procedure of Run No. 11B was designated Sample 113.

The following table compares the results of tests made on Sample 11A and Sample 118.

Durable press ratings after 5 washings Tear strength (Elmendort) Fill Flex abrasion, warp Chlorinated Sam le num er Warp Chlorinated and scorched Chlorine damage-5 washings (tensile) Loss 0! tensilet percen,

TABLE 5 Tensile Wrinkle recovery 1 inch revel Percent elongation Toughness Wrinkle recovery after washing before washing 5 times Sample number Dry 9 296 288 Wet 259 241 Dry 288 276 Wet 250 256 Warp 24 34 Percent retention' Warp Fill 45. 6 113. 7 247. 5

Fill 17. 5 19. 5

Percent of tenisle strength of the untreated fabric retained. after treatment.

EXAMPLE 11 Run No. 11A: Several yards of cellulosic corduroy cloth was padded with Solution llA-an aqueous dimethyloldihydroxyethylene urea solution adjusted to contain about 18% dimethyloldihydroxyethylene urea as TABLE 8 Tensile 1 inch revel Percent retention Wrinkle recovery before washing Wet Sample number Dry Warp

Percent of tensile stren th of the untreated tabrle retained after dissolved solids, about 1% zinc mtrate, about 3.0% of remnant. a non-ionic polyethylene emulsion, and about 0.1% 0

TABLE 7 Durable Crease retention Tear strength press rating (Eimendort) Flex ratings, Sample abrasion, after 5 After 5 number Warp Fill warp washings Initial washings a non-ionic wetting agent also on a solids basis. (Solu- EXAMPLE 12 tion 11A is a conventional ACAnot an improved ACA of our invention.)

The corduroy, which had taken up about 68.5% of its Run No. 12A: A conventional ACA was prepared by the following procedure:

A first mixture was prepared by admixing 152 g. of

water, 208.5 g. of ethyleneurea, and 492.5 g. of an aqueous formaldehyde solution (37% HCHO). The pH of the first mixture was adjusted to 7 by adding aqueous sodium hydroxide solution (20% NaOH) to form a second mixture. The temperature of the second mixture rose to about 40 C., and a 6 g. portion of K CO was added thereto to form a third mixture having a pH of 9.9. The temperature of the third mixture rose to about 55 C. The third mixture was heated to about 60 C. and maintained at this temperature for about 1 hour to form a fourth mixture. The fourth mixture was cooled to about 25 C. and its pH was adjusted to 7.2 by adding acid (ca. 50% aqueous H 50 to form a fifth mixture. The fifth mixture was filtered to remove a somewhat gummy precipitate and the filtrate (a conventional AAC--not an improved ACC of our invention) was admixed with 52 g. of Zn(NO to form a conventional ACAnt an improved ACA of our invention. This conventional ACA was designated Solution 12A.

Run No. 12B: A second conventional ACA was prepared by the general procedure of Run No. 12A; however, in this instance the procedure was modified by: (a) replacing the ethyleneurea with 238 g. of propyleneurea; (b) using 483 g. of the formaldehyde solution; and (c) 34 then cured for minutes at 163 C. The cured sample was labeled Sample 13A.

Three additional runs were made using the general procedure described above but modified in each instance by replacing Solution 12A with the respective solution indicated in the following table, the dissolved solid content of each solution being adjusted to the concentration indicated by dilution with water before padding the cloth sample with solution.

Each of the cured samples of cellulosic broadcloth was numbered with a number corresponding to the run number in which it was prepared. Thus, the sample from Run No. 13B became Sample 13B, that from Run No. 13C became Sample 13C, and that from Run No. 13D became Sample 13D.

Samples 13A, 13B, 13C, and 13D were submitted to the tests listed in the following table and the results were using 149 g. of water. The resulting conventional ACA- 25 as indicated in said table.

TABLE 9 Tensile Wrinkle recovery 1 Inch Ravel Wrinkle recovery after washing Percent elongation Toughness before washing 5 times Pfircent eten- Sample number Dry Wet Dry Wet; Warp tion* Fill Warp Fill Warp Fill Percent of tensile strength of the untreated fabric retained after treatment.

not an improved ACA of our inventionwas designated Solution 12B. TABLE Run No. 12C: An improved ACA of our invention was 40 Tear strength Durable prepared by the following procedure: (Elmendorf) b Flex press rafttings 8. T381011, a er A first mixture was prepared by admixing 152 g. of Sample number Warp Fm Warp washings water, 108 g. of lactamide, 208.5 g. of ethyleneurea, and 492.5 g. of aqueous formaldehyde solution (37% HCHO). 22% lg? g2 :IIIIII The pH of the first mixture was adjusted to 7 by adding 864 817 2,100 2.5 aqueous sodium hydroxide solution NaOH) to form 817 a second mixture. The temperature of the second mixture rose to about 40 C., and a 6 g. portion of K CO was EXAMPLE 14 added thereto to form a third mixture having a pH of 9.9. The temperature of the third mixture rose to about C. The third mixture was heated to about C. and maintained at this temperature for about 1 hour to form a fourth mixture. The fourth mixture was cooled to about 25 C. and its pH was adjusted to 7.2 by adding acid (ca. 50% aqueous H 80 to form a fifth mixture. The fifth mixture was filtered to remove a somewhat gummy precipitate and the filtratean improved AAC of our inventionwas admixed with 52 g. of Zn(NO to form an ACA-an improved ACA of our invention. This improved ACA was designated Solution 12C.

Run No. 12D: A second improved ACA of our invention was prepared by the general procedure of Run No. 11C; however, in this instance the procedure was modified by: (a) replacing the ethyleneurea with 238 g. of propyleneurea; (b) using 483 g. of the formaldehyde solution; (c) using 106 g. of lactamide; and (d) using 149 g. of water. The resulting ACA, an improved ACA of our invention, was designated Solution 11D.

EXAMPLE 13 Run No. 13A: A sample (ca. 76 cm. by 38 cm.) 100% cotton sheeting was padded (ca. 81% wet pickup) with Solution 12A, described supra, after adjusting the dissolved solid content of said Solution 12A to 9% (by dilution with water). The padded sample was placed in a frame to maintain its size and shape, dried for 5 minutes at 93 C., and

Run No. 14A: The general procedure of Run No. 11A, supra, was repeated. However, in this instance the procedure was modified by replacing Solution 11A with a diluted solution (ca. 13% solid content) prepared by diluting several batches of solution made according to the procedure used to prepare Solution 12A. A representative sample of cloth taken from the same bolt as the cloth treated and cured in Run No. 14A was designated Sample 14A.

Run No. 14B: The general procedure of Run No. 11A, supra, was repeated. However, in this instance the procedure was modified by replacing Solution 11A with a diluted solution (ca. 13% solid content) prepared by diluting several batches of solution made according to the procedure used to prepare Solution 12B. A representative sample of cloth taken from the same bolt as the cloth treated and cured in Run No. 14B was designated Sample 14B.

Run No. 14C: The general procedure of Run No. 11A, supra, was repeated. However, in this instance the procedure was modified by replacing Solution 11A with a diluted solution (ca. 13% solid content) prepared by diluting several batches of solution prepared according to the procedure used to prepare Solution 12C. A representative sample of cloth taken from the same bolt as the cloth treated and cured in Run No. 14C was designated Sample 14C.

Run No. 14D: The general procedure of Run No. 11A was repeated. However, in this instance the procedure was modified by replacing Solution 11A with a diluted solution (ca. 13% solid content) prepared by diluting several batches of solution prepared according to the solution used to prepare Solution 12D. A representative sample of cloth taken from the cellulosic corduroy cloth treated and cured in Run No. 14D was designated Sample 14D.

It was noted that samples taken from cellulosic corduroy cloth treated and cured in Runs Nos. 14C and 14D had far better hands than samples taken from cellulosic cloth from the same lot which had been treated and cured in Runs Nos. 14A and 14B.

The following tables report the results of test made on Run No. 15A: A conventional ACA-not an improved ACA of our invention-was prepared by the following procedure:

A 120 g. portion of urea was dissolved in 1650 g. of water in a stirred reaction zone. While stirring the urea solution; (a) 290 g. of an aqueous glyoxal solution (40% glyoxal) was added thereto in five equal portions; and (b) g. of sodium carbonate was also added thereto in five equal portions. After each addition of glyoxal and sodium carbonate the pH of the material in the reaction zone was 4.5. After all of the glyoxal and sodium carbonate was added, the pH of the mixture in the reaction zone was adjusted to 5.5 by adding aqueous sodium hydroxide solution (20% NaOH). The thus formed mixture was heated to 50 C. and maintained at said temperature for 90 minutes. After being maintained at 50 C. for 45 minutes, the pH of the heated mixture had dropped to 5.3. The pH was adjusted to 5.5 by adding a few drops of the aforesaid 20% NaOH solution. At the end of the 90 minute heating period, the pH was determined and found to be 5.5. The thus heated mixture was cooled to 25 C. and 568 g. of an aqueous formaldehyde solution (37% HCHO) added and the pH adjusted to 5.85 with dilute sodium hydroxide solution. The resulting mixture was heated to and maintained at 50 C. for 45 minutes. Said resulting mixture, which had a strong odor of formaldehyde, was cooled to 25 C., and a 82 g. portion of Zn(NO (an acidic catalyst) was added to said mixture and dissolved therein. The resulting ACA (a conventional ACA-not an improved ACA of our invention) was designated Solution 15A.

Run No. 15B: An improved ACAan ACA of our inventionwas prepared by the general procedure of Run No. 15A. However, in this instance the procedure was modified by dissolving 89 g. of lactamide in the aqueous urea solution before adding the glyoxal solution and the sodium carbonate thereto. The final product-an im- 36 proved ACA of our inventionwas designated Solution EXAMPLE 16 cured for 5 minutes at 165 C. The cured sample was designated Sample 16A.

Run No. 168: The general procedure of Run No. 16A was repeated. However, in this instance the procedure was modified by padding a sample of the above-described broadcloth with Solution 15B described supra, after adjusting the dissolved solid content of said Solution 15B to 12.5% (by dilution with water). The padded, dried, and cured broadcloth sample was designated Sample 16B.

Samples 16A and 16B were submitted to the tests listed in the following tables and the results of said tests were as reported in said tables.

TAB LE 13 Wrinkle recovery After Before washing 1 inch revel washing 5 times dry dry Warp Fill Sample number:

TAB LE 14 Tear strength Durable (Elmendort) press ratings Flex abraafter 5 Warp Fill sion-fill washings Sample number:

EXAMPLE 17 Run No. 17A: A conventional aqueous aminoplast paper treating compositionnot an improved aqueous aminoplast treating composition of our inventionwas prepared by the following procedure:

An 8.6 g. portion of ethyleneurea was dissolved in 200 g. of water and 24.3 g. of aqueous formaldehyde solution (37% HCHO) was added thereto. The resulting mixture was heated to 60 C., maintained at this temperature for about /2 hour, and cooled to about 25 C.; the pH of the resulting product, after cooling, was 5.0. The cooled product was designated Solution 17A.

Run No. 17B: The general procedure of Run No. 17A was repeated. However, in this instance the procedure was modified by adding 4.5 g. of lactamide to the ethyleneurea solution before adding the formaldehyde solution. The pH of the productan improved aqueous aminoplast paper treating composition of our inventionafter cooling was 4.2. This product was designed Solution 17B.

Run No. 17C: The general procedure of Run No. 17B was repeated. However, in this instance the procedure was modified by using 8.9 g. of lactamide (rather than the 4.5 g. of Run No. 17B). The pH of the cooled product-an improved aqueous aminoplast paper treating composition of our invention-was 4.1. This product was designated Solution 17C.

Run No. 17D: A conventional aqueous aminoplast paper treating agent-not an improved aqueous aminoplast treating agent of our invention-was prepared by repeating the procedure of Run No. 17A to form a second batch of Solution 17A and dissolving 2 g. of Zn(NO in said second batch of Solution 17A to convert said second batch of Solution 17A into the conventional aminoplast paper treating agent. The pH of this conventional 37 aqueous aminoplast paper treating agent, which was designated Solution 17D, was 5.0.

Run No. 17E: An improved aqueous aminoplast paper treating agent of our invention was prepared by: (a) repeating Run No. 17B to prepare a second batch of Solution 17B; and (b) converting said second batch to the improved aqueous aminoplast paper treating agent by dissolving 2 g. of Zn(NO therein. The pH, at 25 C. Of the resulting improved aqueous aminoplast paper treating agent, which was designated Solution 17B, Was 5.0.

Run No. 17F: An improved aqueous aminoplast paper treating agent of our invention was prepared by; (a) repeating Run No. 17C to prepare a second batch of Solution 17C; and (b) converting said second batch to the improved aqueous arninoplast paper treating agent by dissolving 2 g. of Zn(NO therein. The pH of the resulting improved aqueous aminoplast paper treating agent, which was designated Solution No. 17F, was .0.

EXAMPLE 18 Run No. 18A: A sheet of cellulosic filter paper (Whatman No. 1) was impregnated with Solution 17A-said solution having a solid content of about The impregnated paper was rolled with a 23 pound (10.5 kilogram) brass roller (to remove excess liquid), dried, and cured for an hour at 105-110" C. The treated and cured paper was designated Sample 18A.

Runs No. 18B, 18C, 18D, 18E, and 18F: Five runs were made using the general procedure of the abovedescribed Run No. 18A. However, the procedure was modified by replacing Solution 17A of Run No. 18A with Solutions 17B, 17C, 17D, 17B, and 17F, respectively, as shown in the following table. The designation given resulting samples of treated and cured paper are also shown in the following table.

Sample 18F.

Wet and dry strengths (ASTMD-829) of Samples 18A, 18B, 18C, 18D, 18E, and 1815 were determined. The results obtained and percent of dry strength retained when wet (i.e., (wet strength/dry strength) x 100) are reported in the following table.

TABLE 16 Percent Strength, pounds of dry per inch strength retained Wet Dry when wet Substantially identical results were obtained in other runs where using; (a) dihydroxyethyleneurea or propyleneurea in place of ethyleneurea; (b) N-methylollacetamide,

0 H CHzCHzO H H H ll CH1-CHiC-NH2 in place of lactamide; or (c) adding lactarnide,

to an aminoplast solution which was prepared from ethyleneurea and formaldehyde, propyleneurea and formaldehyde, or dihydroxyethyleneurea and formaldehyde.

EXAMPLE 19 CH CH CHOHCONH was admixed with a mole of formaldehyde (supplied as an aqueous solution (ca. 37% HCHO)) in a stirred reaction zone. The pH of the resulting mixture was adjusted to 7 with aqueous sodium hydroxide (ca. 20% NaOH), :1 1.25 g. portion of sodium carbonate was added and the resulting mixture was heated to 60 0., maintained at said temperature for 2 hours, cooled to room temperature (ca. 25 C.), brought to pH 7 (by adding sulfuric acid), and filtered. The resulting filtrate, an aqueous N-methylol-ahydroxy-n-butyramide solution, was designated Solution Runs No. 19B through 19G: Six additional runs, each using the general procedure of Run No. 19A, supra, were made. However, in each instance the procedure was modified by using one mole of a different hydroxyamide. In each instance the resulting product was the N-methylolamide of the starting amide. The following table shows the amide used in each of said runs and the designation given the resulting N-methylolamide product.

Run No. 20A: Solution 19A was admixed with an aqueous dimethylolethyleneurea (DMEU) solution (45% DEMU)-the two solutions being admixed in such ratio as to provide a resulting first mixture containing N-methylol-a-hydroxy-n-butyramide and DMEU in a mole ratio of 1:1.3. The first mixture was diluted with water and ii) the procedure was modified by replacing Solution 21A with the respective solution indicated in the following table which also shows the designation assigned to each cured sample.

TABLE 19 ACA Designation given padding resulting cured Run No. solution sample 21B 2013 Sample 21B.

200 Sample 21C. 20D Sample 21D. 20E Sample 21E.

20F Sample 21F. 21G 20G Sample 21G.

EXAMPLE 22 Samples 21A through 216 were submitted to the tests listed in the following table and the results of said tests were as stated in said table.

TABLE 20 Ravel strip tensile, pounds Flex abrasion, cycles Chlorine Durable damage, press Initial After 5 washings Initial, .altlter 5 percent ratings warp was ings stren th after 5 Sample No. Warp F111 Warp Fill warp 1%ss washes Control sample 28 18 26 20 151 107 7 3. 5 21A 33 23 31 27 184. 202 3. 5 27 32 24 192 230 0 3. 5 32 2? 28 23 165 179 3. 5 32 2o 30 23 251 278 7 3. 5 32 20 32 18 116 131 3 +3. 5 30 20 27 23 108 203 +3. 0 31 26 31 26 259 241 +3. 0

admixed with zinc nitrate and Tergitol NPX wetting agent (a phenyl ether of polyethyleneglycol) to form an ACA solution having a DMEU content of 7.5%, a Zn(NO content of 1.5%, a Tergitol NPX content of 0.1%, and a N-methylol a hydroxy n bntyramide to DMEU mole ratio of 1: 1.4. The pH of this ACA solution was adjusted to 5-6 by adding 10% acetic acid thereto to form an ACA padding solution which was designated Solution 20A.

Runs No. 2013 through 20G: Six additional runs, each using the general procedure of Run No. 20A, supra, were made. However, in each instance the procedure was modified by replacing the Solution 19A of Run 20A with a different solution (Solutions 19B through 19F, respectively) prepared in Example 19, supra. In each instance the mole ratio (in the resulting ACA solution) of dimethylol compound formed in Example 19 to DMEU was 1: 1.3, and in each instance the ACA solution contained 7.5% dimethylolethyleneurea, 1.5% Zn(NO and 0.1% of the aforesaid Tergitol NPX wetting agent. The following table shows the solutions from Example 19 used in each of these runs and the designation given to each of the resulting ACA padding solutioneach padding solution being formed by adjusting the pH of the corresponding ACA solution to 5-6 with 10% acetic acid.

TABLE 18 Designation given Starting solution resulting ACA From Example 19: padding solution Solution 19B Solution 20B. Solution 19C Solution 20C. Solution 19D Solution 20D. Solution 19E Solution 20E. Solution 19F Solution 20F. Solution 19G Solution 20G.

EXAMPLE 21 Run No. 21A: A sample (ca. 76 cm. by 38 cm.) of cotton combed lawn was padded through ACA Padding Solution 20A to an 80% Wet pickup. The padded sample was placed in a frame to maintain its size and shape, dried, for 5 minutes at 93 C., and then cured for 5 minutes at 163 C. The cured sample was designated Sample 21A.

Six additional runs were made using the general procedure of Run No. 21A, supra. However, in each instance The sample designated Control Sample in Table 20 was prepared by: (a) padding a sample (ca. 76 cm. by 38 cm.) of combed cotton lawn from the same lot used to prepare Samples 22A through 226 with an 80% wet takeup (pickup) of an ACA padding solution prepared by: (i) forming an ACA solution having a DMEU content of 7.5%, a Zn(NO content of 1.5%, and a Tergitol NPX content of 0.1%; and (ii) adjusting the pH thereof to 5-6 with 10% acetic acid; (b) placing the padded sample in a frame to maintain its size and shape; (0) drying the thus formed sample for 5 minutes at 93 C.; and (d) curing the dried sample by maintaining it at 163 C. for 5 minutes. Tergitol NPX is an alkyl phenyl ether of polyethylene glycol; it (said Tergitol) is a surface active agent.

Another series of runs was made using the general procedure of Example 22 but modifying said procedure by replacing each sample (Samples 22A through 22G) with a sample prepared by padding (80% wet pickup) cloth from the same lot used in Example 21 with an ACA padding solution prepared according to the general procedure of Example 20 except that, in each instance, the N-methylolamide component used in preparing the ACA padding solution in Example 20 was replaced with the corresponding amide (e.g., the N-methylol-a-hydroxy-nbutyramide of Run 20A was replaced with u-hYdIOXY- n-butyramide).maintaining a mole ratio of amide to DMEU of 1:1.4 in the resulting ACA padding solution. The padded cloth was placed in a frame, dried at 93 C. for 5 minutes, and then cured at 163 C. for 5 minutes. The following amides were used in these runs:

CH3CH2CHOHCONH2 cn cnoncorvn (CH3)2COHCONH2 CH3CHOHCONHCH3 cn ononconncn cn on CH3CHOHCONH(CH2)3CH3 nocn colvn In the instance of each of the thus treated cloth samples the results of tests corresponding to those reported in Table 20, supra, were substantially identical with those reported for the corresponding sample (i.e., the sample prepared from the ACA padding solution containing the corresponding N-methylolamide) in said table. These. 

